EP1064333B1 - Compositions de revetement et procedes - Google Patents

Compositions de revetement et procedes Download PDF

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Publication number
EP1064333B1
EP1064333B1 EP99909094A EP99909094A EP1064333B1 EP 1064333 B1 EP1064333 B1 EP 1064333B1 EP 99909094 A EP99909094 A EP 99909094A EP 99909094 A EP99909094 A EP 99909094A EP 1064333 B1 EP1064333 B1 EP 1064333B1
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EP
European Patent Office
Prior art keywords
composition
top coat
undercoat
groups
synthetic resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99909094A
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German (de)
English (en)
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EP1064333A1 (fr
Inventor
Peter Carson
Joanne France
Rodney Ralph Brooks
Michael Fowler
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PRC Desoto International Inc
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PRC Desoto International Inc
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Publication of EP1064333A1 publication Critical patent/EP1064333A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers

Definitions

  • This invention relates to the application to a substrate of a coating system in which a cured primer coating is overcoated with a top coat which is intended to be strippable, that is to say removable from the primed substrate by a paint stripping composition without removal of the primer from the substrate.
  • a coating system in which a cured primer coating is overcoated with a top coat which is intended to be strippable, that is to say removable from the primed substrate by a paint stripping composition without removal of the primer from the substrate.
  • Such coating systems are widely used on aircraft and may also be used on other substrates, for example commercial vehicles, cars, yachts or railway vehicles.
  • the cured primer and top coat must resist water and certain organic solvents such as aviation fuel and preferably also resist hydraulic fluids based on phosphate esters such as tricresyl phosphate or tri-n-butyl phosphate, e.g. that sold under the trade mark "Skydrol".
  • phosphate esters such as tricresyl phosphate or tri-n-butyl phosphate, e.g. that sold under the trade mark "Skydrol”.
  • Each coating is generally cured by the reaction of components which have been packaged separately and are mixed at or shortly before application. When an aircraft is to be repainted it is usual to remove at least the top coat using a paint stripper before repainting.
  • the preferred stripping compositions used nowadays are based on aqueous benzyl alcohol with additives such as acidic (formic or oxalic acid) or alkaline (to pH 11 or 12) or neutral additives, although some halogenated solvents such as methylene chloride with phenol are still used.
  • the top coat adheres to the primer so strongly that the top coat cannot be stripped without removing cr at least damaging the primer.
  • Aircraft owners and operators would prefer a paint system in which the primer remained on the aircraft to prevent the stripping composition contacting any resins, sealants or adhesives used in the aircraft construction or the metallic substrate and to avoid repeating the pre-treatment and primer coating of the aircraft.
  • GB-A-1511935 describes a strippable coating system comprising a non-crosslinked polyamide intermediate coating between the primer and the top coat. This at least partially resists the solvent used to remove the top coat and can itself easily be removed by alcohol-based solvents to reveal the primer.
  • DE-A-2528943 describes a linear non-crosslinked elastic polyurethane coating used between crosslinked polyurethane primer and top coat layers.
  • EP-A-147984 describes a barrier intermediate coating comprising a film-forming addition polymer comprising units of a vinyl aromatic monomer and units of a monomer containing a hydroxy alkyl group in an amount to provide a hydroxyl content of the addition polymer in the range 0.5 to 5 per cent by weight reacted with a polyisocyanate containing at least 2 isocyanate groups per molecule.
  • WO-A-98/13148 describes a process for overcoating a substrate having a cured primer coating with a curable top coat which when cured is swellable by a stripping composition, in which process a non-volatile polar material having high affinity for the primer surface is applied to the primed substrate from an aqueous liquid vehicle before coating with the top coat, whereby the said polar material facilitates the removal of the top coat from the primer by the stripping composition.
  • EP-A-14597 describes a paint undercoat in which the film-forming resin has an acid value of from 10 to 45 mg KOH/g. Paint films including such an undercoat are stripped by means of a paint stripper having a pH of from 8 to 14 which attacks the undercoat paint film.
  • non-volatile polar materials used in the process of WO-A-98/13148 can also facilitate selective stripping of a top coat from an undercoat when they are included in one of the coating compositions.
  • an undercoat composition which comprises a film-forming synthetic resin is characterised in that the undercoat composition contains a non-volatile acidic aromatic polar organic compound in free acid or salt form, which compound facilitates the removal by a stripping composition of a top coat paint which is subsequently applied over the undercoat.
  • the synthetic resin contains functional groups whereby it is curable and the undercoat composition also contains a curing agent for crosslinking the synthetic resin.
  • a coating process comprises applying to a substrate an undercoat composition (preferably a curable undercoat composition which is then cured), applying a curable top coat composition over the undercoat and curing the top coat, the cured top coat being swellable by a stripping composition, and it is characterised in that the undercoat composition contains a non-volatile acidic aromatic polar organic compound in free acid or salt form, which compound facilitates the removal of the top coat from the undercoat by the stripping composition.
  • the undercoat composition can for example be an anticorrosive primer composition. This is particularly advantageous since a full, strippable, coating system can be formed from only two coating layers. Alternatively, the undercoat composition can be applied as an intermediate layer over a cured anticorrosive primer composition before a curable top coat composition is applied.
  • the synthetic resin is an epoxy resin and the curing agent contains amine groups
  • the curing agent may be an amino-functional polyamide and/or an araliphatic diamine or an alkylene, arylene or alkarylene diamine.
  • the curing agent can alternatively contain carboxylic acid groups, or alternatively the synthetic resin may contain carboxylic acid or amine groups with the curing agent containing epoxide groups.
  • the primer can be a thermosetting polyurethane primer in which the synthetic resin contains hydroxyl groups and the curing agent contains blocked or unblocked isocyanate groups or the synthetic resin contains blocked or unblocked isocyanate groups and the curing agent contains hydroxyl groups.
  • the primer coating can be applied from solution or dispersion in an organic solvent or can be a high solids or solventless composition or may be an aqueous composition such as a dispersion, emulsion or solution or may be a water-thinnable primer.
  • the undercoat composition is an intermediate layer, it is preferably a curable coating composition which is cured before the top coat is applied.
  • a curable composition can for example be based on an epoxy resin with an amino-functional curing agent or on a thermosetting polyurethane as described above.
  • the intermediate layer is most preferably based on a curable resin system which resists stripping solvent, so that it can be overcoated after stripping of the top coat.
  • the intermediate layer can be based on a thermoplastic resin, for example a thermoplastic polyester, polyurethane, fluoropolymer, acrylic polymer or polyamide.
  • the intermediate layer can be a high-solids or solventless composition or can be applied from solution or dispersion in water and/or an organic solvent, for example a thermoplastic resin-based coating can be applied from aqueous dispersion or from a dispersion in water and organic solvent.
  • a water-containing dispersion may for example contain a compound which facilitates the formation of the dispersion, such as a surfactant, which is volatile or is reactive with a component of the coating composition, so that it does not remain in the coating film as a low molecular weight compound but evaporates from it or reacts with it on curing.
  • a nitroparaffin for example, can be used as a volatile surfactant.
  • the acidic aromatic polar organic compound is preferably a non-polymeric organic compound having a molecular weight in the range 120 to 1500.
  • the acidic aromatic compound generally contains at least one acidic group such as a carboxylic acid group or sulphonic acid or phosphonic acid group present in free acid form or in salt form (in which case the compound may no longer be acidic).
  • the salt may be an amine salt of a primary, secondary or tertiary amine or an alkali metal or ammonium salt.
  • the acidic group is preferably attached directly to an aromatic ring. Many of the effective compounds additionally contain at least one hydroxy group and/or amino group.
  • the acidic aromatic compound preferably has a molecular weight in the range 120 or 150 up to about 1000 or 1500.
  • gallic acid (3,4,5-trihydroxybenzoic acid), which is not generally regarded as a dye.
  • Amine salts of gallic acid are particularly preferred.
  • 2,5-Dihydroxybenzoic acid is also effective, although 3,5-dihydroxybenzoic acid is much less effective in giving stripping.
  • 1,2-Dihydroxybenzene-3,5-disulphonic acid is also effective in giving selective stripping.
  • acidic dyes which have been found effective in giving selective stripping are Catechol Violet, Fast Green, Lissamine Green SF, Orange G, Amido Black, Methyl orange, sulphonyl porphyrins, for example 5, 10, 15, 20-tetrakis (4-sulphonatophenyl)-porphine manganese (III) chloride of molecular weight 1023, bromocresol purple, calcion (a sulphonate-functional dye), fluorescent brightener 28 (an optical brightener), Nigrosin (Acid Black 2), Brilliant Black BN, citrazinic acid, xylenol blue Na salt, Reactive Blue 2, xylenol orange Na salt, Brilliant Blue R, Brilliant Blue G and chromoxane cyanine R.
  • Catechol Violet Fast Green
  • Lissamine Green SF Lissamine Green SF
  • Orange G Amido Black
  • Methyl orange sulphonyl porphyrins
  • Aurin which is an acid dye although it does not contain any carboxylic or stronger acid groups, is also moderately effective.
  • Mixtures of acidic aromatic materials can be used, for example mixtures of gallic acid with a dye such as Fast Green.
  • Other examples of acid-functional acidic aromatic polar materials which have given selective stripping are a hyperbranched poly(5-hydroxyisophthalic acid) and poly(styrene sulphonate).
  • the acidic aromatic compound can be used in free acid form or can be added as a preformed salt, or a salt of the acidic aromatic compound can be formed in situ in the composition; for example an amine salt can be formed by adding the amine and the acidic aromatic compound to the coating composition.
  • the dye Safranine O having the structure: where each R represents methyl and X- is chloride, which does not contain any acidic groups, has also been found to be effective and its use is also covered by the present invention, although other dyes containing amine or hydroxyl groups with no acidic groups, such as malachite green, night blue and crystal violet, have been found to be ineffective.
  • R is hydrogen or another lower (1-4C) alkyl group and/or X - is another anion
  • the acidic aromatic compound is preferably present at a concentration of at least 0.01% by weight, most preferably at least 0.05% or 0.1% by weight, in the coating composition as applied and preferably at least 0.05% by weight, most preferably at least 0.1% or 0.2% by weight, in the dry coating to give the desired ease of removal of the top coat by the stripping composition.
  • the level of acidic aromatic compound is preferably below 4% by weight, more preferably below 2% and most preferably below 1% by weight, of the wet coating composition (below 10%, most preferably below 5 or 2%, by weight of the dry coating) for an anticorrosive primer composition. Higher levels have also been found to provide strippability of the top coat, but care must be taken not to adversely affect the other properties of the primer.
  • An undercoat composition according to the invention which is an anticorrosive primer generally contains an anticorrosive pigment such as a chromate, phosphate, phosphonate or molybdate or a pigment as described in WO 97/13888 and may contain one or more other pigments and/or fillers.
  • an anticorrosive primer is generally applied at 5-100 ⁇ m dry film thickness.
  • the primer is generally stored as a 2- or 3-pack composition, with the film-forming resin and the curing agent being stored in separate packages and in some cases catalyst and/or additives being stored as a third package, all the packages to be mixed shortly before application of the coating to the substrate.
  • the acidic aromatic compound can in general be included in any of the packs of such a coating.
  • a 3-pack composition it is preferably included with the catalyst and additives.
  • the acidic aromatic compound is preferably packaged with the amine, and in a 2-pack polyurethane it is preferably packaged with the hydroxy-functional component.
  • the level of acidic aromatic compound is generally below 5% by weight of the wet coating composition and below 10% by weight of the dry coating, and it is preferably below 1 to 2% by weight of the wet coating.
  • the interlayer coating can be formulated as an additional anticorrosive primer layer containing anticorrosive pigment, or it can be formulated similarly to a top coat with opacifying pigment, or it can simply contain a film-forming resin and the acidic aromatic compound, optionally with one or more fillers or inert pigments.
  • the interlayer coating can for example be applied at 1 to 100 ⁇ m, preferably 5 to 25 ⁇ m, dry film thickness.
  • the top coat paint which is applied over an undercoat composition of the invention is generally a curable coating comprising at least two co-reactive components, which are usually packaged separately and mixed at application (for example by a twin-feed spray) or shortly before application (for example up to 8 hours before).
  • the top coat paint particularly for aircraft coatings, is preferably a polyurethane such as a polyester-urethane, although other curable paints such as polyester, fluoropolymer or acrylic polymer paints, including reactive acrylic polymer systems based on oxazolidine functionality, may be used.
  • the top coat paint is preferably applied from organic solvent solution, including high solids formulations, but it can in general be applied from dispersion in water and/or organic solvent or as a solventless (100% solids) composition.
  • a top coat composition comprises a film-forming synthetic resin having functional groups and a curing agent for crosslinking the synthetic resin and is characterised in that the top coat composition contains a non-volatile acidic aromatic polar organic compound in free acid or salt form, which compound facilitates the removal of the cured top coat by a stripping composition from a cured undercoat of similar composition which does not contain the said acidic aromatic polar organic compound.
  • a process for overcoating a substrate having a cured primer coating with a curable top coat composition which when cured is swellable by a stripping composition is characterised according to this aspect of the invention in that a first layer of the top coat composition is applied to the primed substrate and cured and a second layer of the top coat composition containing a non-volatile acid aromatic polar organic compound in free acid or salt form is coated over the first layer and cured, whereby the subsequent removal of the second layer from the first layer by the stripping composition is facilitated.
  • the top coat is strippable from an intermediate layer applied over an anticorrosive primer, for example a relatively temporary decorative coating applied over a permanent coating layer.
  • a top coat composition according to the invention containing an acidic aromatic compound in a cured polyurethane top coat can be stripped from an intermediate layer (first top coat layer) of similar composition.
  • the top coat composition can for example be based on a synthetic resin containing hydroxyl groups and a curing agent containing blocked or unblocked isocyanate groups, or on a synthetic resin containing blocked or unblocked isocyanate groups and a curing agent containing hydroxyl groups.
  • the top coat composition can alternatively be based on a polyester, fluoropolymer or acrylic polymer, for example an oxazolidine-functional acrylic polymer. Both layers of the top coat composition are in general pigmented with one or more opacifying pigments, for example titanium dioxide or a colour pigment such as phthalocyanine.
  • opacifying pigments for example titanium dioxide or a colour pigment such as phthalocyanine.
  • the coating composition of the invention can in general be based on other curing chemistries.
  • the synthetic resin may contain activated -CH- groups bonded to at least two electron-withdrawing groups with a curing agent containing blocked or unblocked amine groups, epoxide groups or acrylic or methacrylic groups, or the synthetic resin may contain acrylic or methacrylic groups, epoxide groups or blocked or unblocked amine groups with a curing agent containing activated -CH- groups.
  • the preferred activated -CH- groups are acetoacetate groups, although malonate ester, 1,3-diketone or cyanoacetate groups are alternatives.
  • a synthetic resin containing acetoacetate groups can be used with a curing agent containing blocked or unblocked amine groups.
  • An epoxy resin can be used with a curing agent containing acetoacetate groups.
  • a synthetic resin containing acrylic or methacrylic groups, for example a urethane acrylate, can be used with a curing agent containing acetoacetate groups.
  • the synthetic resin contains anhydride groups and the curing agent contains hydroxyl groups or the synthetic resin contains hydroxyl groups and the curing agent contains anhydride groups.
  • the acidic aromatic compound used in the top coat composition of the invention can in general be any of those listed above for use in an undercoat, and it is used in free acid or salt, for example amine salt, form.
  • the acidic aromatic compound is preferably present in the top coat paint at a concentration of at least 0.01% by weight, more preferably at least 0.05% and most preferably at least 0.1% by weight, of the coating composition (at least 0.05%, preferably at least 0.2%, by weight of the dry coating) up to 2% or 4% by weiqht of the coating composition (4 or 10% by weight of the dry coating).
  • the top coat composition of the invention is usually a 2-pack or 3-pack composition, and the acidic aromatic compound can be packaged in any of the packs as described above in connection with primers.
  • the coating composition of the invention can alternatively be a single pack composition cured by moisture, oxygen, heat (for example a powder coating), UV, electron beam or laser radiation or by application of curing agent vapour.
  • An undercoat composition according to the invention can be applied by extrusion coating or as a preformed film.
  • the top coat After the top coat has been allowed to cure, preferably for at least 3 days, it adheres firmly to the primer, and the coating system is resistant to spraying with salt-laden water and to immersion in "Skydrol" phosphate ester and generally to immersion in water, so that neither separation of the top coat from the primer or undercoat nor significant blistering occurs.
  • the top coat is treated with a paint stripper in which it swells, particularly a stripper of a type used commercially to strip aircraft paints, swelling of the top coat is followed by detachment from the primer or undercoat. The top coat lifts off the primer and may fall right away or is readily removed by low-pressure water washing.
  • the top coat can readily be removed within a time which is generally 10 minutes to 5 hours and usually 0.5 to 2 hours after application of the paint stripper, without any removal of the primer or of a cured interlayer undercoat.
  • the primer or cured undercoat may be somewhat swollen or discoloured by the paint stripper, but it resists removal with the top coat and continues to adhere to the substrate. Any swelling of the primer or undercoat subsides as the paint stripper dries.
  • the stripper most widely used to strip aircraft paints, particularly polyurethane top coats is an aqueous thickened mixture of benzyl alcohol and formic acid.
  • Alternative strippers are alkaline thickened aqueous benzyl alcohol or a stripper based on methylene chloride and phenol (used to strip certain fluoropolymer and acrylic top coats).
  • the primer/undercoat can be recoated with a fresh top coat.
  • an undercoat composition according to the invention can be recoated with a fresh top coat and, after use in service, the fresh top coat can in its turn be readily stripped from the undercoat by a stripping solvent, allowing further repainting with top coat.
  • Aluminium panels were chromic acid pickled and sprayed with 15-20 ⁇ m of a high-solids (volatile organic content (VOC) 360 g/l) primer based on a liquid bisphenol F epoxy resin containing anticorrosive pigments and an amine curing agent, applied from organic solvent solution, and allowed to cure at ambient temperature.
  • VOC volatile organic content
  • a solution of gallic acid dissolved in acetone was added with stirring, so that the final concentration of gallic acid in the mixed wet paint was 0.2% by weight.
  • the primed panels were topcoated with 40 - 50 ⁇ m dry film thickness of a pigmented polyurethane topcoat applied from an organic solvent blend.
  • the topcoat was a 2-pack polyurethane of a type commonly used for aircraft, comprising a hydroxy-functional polyester component and an aliphatic polyisocyanate component. The topcoat was allowed to cure under ambient conditions for one week before being tested for selective strippability and chemical resistance.
  • topcoat was then readily removed with a low-pressure water wash used to clean off the stripping formulation, leaving a clean intact primer surface.
  • Example 1 The process of Example 1 was repeated with a high-solids, bisphenol A-based epoxy primer containing anticorrosive pigments reacted with an amine curing agent, applied from organic solution. Gallic acid dissolved in acetone was added at 0.2% by weight gallic acid based on the primer. The primer was overcoated after 20 hours with 60 ⁇ m of the topcoat applied in Example 1. The panels were air dried for 7 days.
  • topcoat was then readily removed with a low-pressure water wash used to clean off the stripping solvent, leaving a clean intact primer surface.
  • a solution of gallic acid was neutralised to pH6 with ammonia solution and added dropwise with stirring to the epoxy component of a pigmented paint formulation based on the epoxy resin of Example 1, containing no anticorrosive pigments, cured with an amine curing agent, and applied from organic solvent solution.
  • the concentration of gallic acid ammonium salt in the mixed wet paint was equal to 0.2% by weight gallic acid.
  • the paint containing the amine salt of gallic acid described above was sprayed onto the anticorrosive epoxy primer with a film thickness of 15-18 ⁇ m.
  • the intermediate coat was allowed to dry for 5 hours at ambient conditions. 40-60 ⁇ m of the topcoat as used in Example 1 was sprayed on top.
  • the panels were air dried for 3 days and force dried at 70°C for 3 hours.
  • Panels were found to be resistant to immersion in Skydrol at 70°C for 7 days and in water at 23°C for 7 days.
  • Chromic acid pickled aluminium panels were coated with 15-20 ⁇ m of either a high-solids epoxy primer as in Example 1 or a conventional solids epoxy primer as in Example 3, containing anticorrosive pigments, reacted with an amine curing agent, applied from organic solvent solution and allowed to cure at ambient temperature.
  • the epoxy primer was allowed to dry for 4 hours before overcoating with an intermediate coating formulation containing the triethanolamine salt of gallic acid.
  • the intermediate formulation contained a mixture of an aqueous polyurethane dispersion and an aqueous acrylic dispersion into which was added 2g (per 100g of polymer dispersion)of pre-manufactured triethanolamine salt of gallic acid in water.
  • the intermediate formulation also contained rheology modifiers and flow additives and had a VOC of 370 g/l.
  • the intermediate formulation was applied at 20 ⁇ m dry film thickness.
  • the scheme was allowed to cure at ambient temperature for one week before being tested for selective strippability and chemical resistance.

Abstract

L'invention concerne une composition de sous-couche. Cette composition comprend une résine synthétique feuillogène et contient un composé organique polaire aromatique acide non volatile, sous forme de sel ou d'acide libre. Ce composé permet d'enlever plus facilemen, à l'aide d'une composition de dépouillage, une couche de finition qui est appliquée ultérieurement sur la sous-couche. Une composition de finition prévue pour être appliquée comme couche extérieure sur un substrat comprend une résine synthétique feuillogène comportant des groupes fonctionnels et un agent de durcissement pour assurer la réticulation de la résine synthétique, et un composé organique polaire aromatique acide non volatile sous forme de sel ou d'acide libre. Ce composé permet d'enlever plus facilement la couche de finition durcie par une composition de dépouillage à partir d'une sous-couche durcie de même composition qui ne contient pas ledit composé organique polaire aromatique acide.

Claims (29)

  1. Composition de sous-couche pour revêtir un substrat, laquelle sous-couche comprend une résine synthétique filmogène, caractérisée en ce que la composition de sous-couche contient un composé organique polaire aromatique acide non volatil sous forme d'acide libre ou de sel, lequel composé facilite le retrait par une composition de décapage d'une peinture de couche de finition qui est appliquée ultérieurement sur la sous-couche.
  2. Composition de sous-couche selon la revendication 1, caractérisée en ce que la résine synthétique a des groupes fonctionnels grâce auxquels elle est durcissable et la composition contient un durcisseur pour réticuler la résine synthétique.
  3. Composition de sous-couche selon la revendication 1, caractérisée en ce que la résine synthétique est une résine époxyde et le durcisseur contient des groupes aminés ou acide carboxylique, ou la résine synthétique contient des groupes aminés ou acide carboxylique et le durcisseur contient des groupes époxyde.
  4. Composition de couche de finition destinée à être appliquée comme revêtement extérieur sur un substrat, laquelle composition de couche de finition comprend une résine synthétique filmogène ayant des groupes fonctionnels et un durcisseur pour réticuler la résine synthétique, caractérisée en ce que la composition de couche de finition contient un composé organique polaire aromatique acide non volatil sous forme d'acide libre ou de sel, lequel composé facilite le retrait de la couche de finition durcie par une composition de décapage à partir d'une sous-couche durcie de composition semblable qui ne contient pas ledit composé organique polaire aromatique acide.
  5. Composition de couche de finition selon la revendication 4, caractérisée en ce que la résine synthétique est un polyester, un fluoropolymère ou un polymère acrylique.
  6. Composition selon la revendication 2 ou selon la revendication 4, caractérisée en ce que la résine synthétique contient des groupes hydroxyle et le durcisseur contient des groupes isocyanate bloqués ou non bloqués, ou la résine synthétique contient des groupes isocyanate bloqués ou non bloqués et le durcisseur contient des groupes hydroxyle.
  7. Composition selon la revendication 2 ou selon la revendication 4, caractérisée en ce que la résine synthétique contient des groupes -CH- activés liés à au moins deux groupes accepteurs d'électrons et le durcisseur contient des groupes aminés bloqués ou non bloqués, des groupes époxyde ou des groupes acryliques ou méthacryliques, ou la résine synthétique contient des groupes acryliques ou méthacryliques, des groupes époxyde ou des groupes aminés bloqués ou non bloqués et le durcisseur contient des groupes -CH- activés liés à au moins deux groupes accepteurs d'électrons.
  8. Composition selon la revendication 2 ou la revendication 4, caractérisée en ce que la résine synthétique contient des groupes anhydride et le durcisseur contient des groupes hydroxyle, ou la résine synthétique contient des groupes hydroxyle et le durcisseur contient des groupes anhydride.
  9. Composition selon l'une quelconque des revendications 1 à 8, caractérisée en ce que le composé aromatique acide est un composé organique non polymère ayant une masse moléculaire dans la plage allant de 120 à 1 500.
  10. Composition selon l'une quelconque des revendications 1 à 9, caractérisée en ce que le composé aromatique contient au moins un groupe acide carboxylique.
  11. Composition selon l'une quelconque des revendications 1 à 10, caractérisée en ce que le composé aromatique contient au moins un groupe acide sulfonique.
  12. Composition selon la revendication 10 ou la revendication 11, caractérisée en ce que le composé aromatique contient en outre au moins un groupe hydroxy et/ou un groupe amino.
  13. Composition selon la revendication 12, caractérisée en ce que le composé aromatique est de l'acide gallique.
  14. Composition selon l'une quelconque des revendications 1 à 12, caractérisée en ce que le composé aromatique acide est présent sous forme de sel aminé.
  15. Composition selon l'une quelconque des revendications 1 à 14, caractérisée en ce que le composé aromatique acide y est présent à une concentration de 0,05 à moins de 1 % en poids.
  16. Procédé pour revêtir un substrat consistant à appliquer au substrat une composition de sous-couche durcissable et à durcir la sous-couche, et à appliquer une composition de couche de finition durcissable sur la sous-couche et à durcir la couche de finition, la couche de finition durcie étant capable de gonfler par une composition de décapage, caractérisé en ce que la composition de sous-couche contient un composé organique polaire aromatique acide non volatil sous forme d'acide libre ou de sel, lequel composé facilite le retrait de la couche de finition de la sous-couche par la composition de décapage.
  17. Procédé selon la revendication 16, caractérisé en ce que la composition de sous-couche est une composition de couche primaire anticorrosion.
  18. Procédé selon la revendication 16 ou 17, caractérisé en ce que le composé aromatique acide est présent à une concentration de 0,05 à moins de 1 % en poids dans la composition de couche primaire.
  19. Procédé selon la revendication 16, caractérisée en ce que la composition de sous-couche est appliquée en tant que couche intermédiaire sur une composition de couche primaire anticorrosion durcie avant que la composition de couche de finition durcissable ne soit appliquée.
  20. Procédé pour recouvrir un substrat ayant un revêtement primaire durci afin de faciliter le retrait par une composition de décapage d'une couche de finition appliquée ultérieurement, caractérisé en ce qu'une composition de revêtement comprenant une résine filmogène et un composé organique polaire aromatique acide non volatil sous forme d'acide libre ou de sel, lequel composé facilite ledit retrait de la couche de finition, est appliquée sur le revêtement primaire durci avant que la couche de finition ne soit appliquée.
  21. Procédé selon la revendication 20, caractérisé en ce que ladite composition de revêtement est une composition de revêtement durcissable et est durcie avant que la couche de finition ne soit appliquée.
  22. Procédé selon la revendication 20, caractérisé en ce que ladite composition de revêtement comprend une résine synthétique thermoplastique.
  23. Procédé selon l'une quelconque des revendications 20 à 22, caractérisé en ce que ladite composition de revêtement est appliquée à partir d'une dispersion aqueuse.
  24. Procédé selon la revendication 23, caractérisé en ce que la dispersion aqueuse contient un surfactant volatil ou réactif qui facilite la formation de la dispersion et qui s'évapore du revêtement à l'application ou réagit avec la composition de revêtement au durcissement.
  25. Procédé selon l'une quelconque des revendications 20 à 24, caractérisé en ce que le composé aromatique acide est présent à une concentration de 0,05 à moins de 5 % en poids dans ladite composition de revêtement.
  26. Procédé pour recouvrir un substrat ayant un revêtement primaire durci avec une composition de couche de finition durcissable qui, lorsqu'elle est durcie, est capable de gonfler par une composition de décapage, caractérisé en ce qu'une première couche de la composition de couche de finition est appliquée au substrat apprêté et durcie, et une seconde couche de la composition de couche de finition contenant un composé organique polaire aromatique acide non volatil sous forme d'acide libre ou de sel, est appliquée sur la première couche et durcie, moyennant quoi le retrait ultérieur de la seconde couche de la première couche par la composition de décapage est facilité.
  27. Procédé selon la revendication 26, caractérisé en ce que le composé aromatique acide est présent à une concentration de 0,05 à moins de 1 % en poids dans la composition de couche de finition appliquée en tant que seconde couche.
  28. Procédé selon l'une quelconque des revendications 16 à 27, caractérisé en ce que le composé aromatique acide est défini selon l'une quelconque des revendications 9 à 15.
  29. Procédé pour revêtir un substrat consistant à appliquer au substrat une composition de sous-couche, à appliquer une composition de couche de finition durcissable sur la sous-couche et à durcir la couche de finition, la couche de finition durcie étant capable de gonfler par une composition de décapage, caractérisé en ce que la composition de sous-couche contient un composé de la structure
    Figure 00340001
       où chaque R représente un atome hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone et X- représente un anion, lequel composé facilite le retrait de la couche de finition de la sous-couche par la composition de décapage.
EP99909094A 1998-03-18 1999-03-16 Compositions de revetement et procedes Expired - Lifetime EP1064333B1 (fr)

Applications Claiming Priority (3)

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GB9805836 1998-03-18
GBGB9805836.5A GB9805836D0 (en) 1998-03-18 1998-03-18 Coating compositions and processes
PCT/GB1999/000777 WO1999047613A1 (fr) 1998-03-18 1999-03-16 Compositions de revetement et procedes

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US8231970B2 (en) * 2005-08-26 2012-07-31 Ppg Industries Ohio, Inc Coating compositions exhibiting corrosion resistance properties and related coated substrates
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CN105164315A (zh) * 2013-03-16 2015-12-16 Prc-迪索托国际公司 作为缓蚀剂的唑类化合物
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GB9805836D0 (en) 1998-05-13
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CN1293702A (zh) 2001-05-02
BR9908979A (pt) 2000-11-14
ES2226350T3 (es) 2005-03-16
CN1136276C (zh) 2004-01-28
CA2322632A1 (fr) 1999-09-23
DE69919340T2 (de) 2005-08-11
AU759959B2 (en) 2003-05-01
DE69919340D1 (de) 2004-09-16
KR20010041896A (ko) 2001-05-25
AU2846399A (en) 1999-10-11
WO1999047613A1 (fr) 1999-09-23
US6899924B1 (en) 2005-05-31

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